Alumina gel pellets



. Patented Me, 24,1949 u "UNITED STATES PATENT OFFICE ALUMINA GEL PELL'ETS Joseph U. Messenger, Dallas, Tex., assignor, by mesne assignments, to Socony-Vacuum Oil Company, Incorporated, New York, N. Y., a corporation of New York No Drawing. Application May 23,1947, Serial No. 750,171

10 Claims. (Cl. 252-448) This invention relates to themanufacture of relatively large spheres, it has not been successsolid catalysts and relates more particularly to fully employed for the formation of relatively the manufacture of alumina catalysts in the form small spheres. Thus when this method is em- I of relatively small spherical or spheroidal parployed for the purpose of folimin k elatively small u e e; -s w s sphers;such 'as"spheres, after drying and acti- Alumina catalysts have found extensive use in vating, having diameters not greater than about various types of hydrocarbon conversion proc-' one millimeter, for example, by extruding the esses and in these processes the catalyst may be hydrosol under conditions to form small globules employed as a fixed bed or as a. movingbed. into the water-immisciblelayer, the globules tend While the catalyst may be employed in various ,to distort and agglomerate at the interface beshapes, it has been found that the most desirable tween the two liquid bodies to form large, irregshapes are spheres since in fixed bed operations ular masses rather than descend to the lower the catalyst will uniformly pack in the reaction setting layer in their original form of small,

zone and thereby minimize the possibility of is rete Spheres. channeling of the hydrocarbon reactants and ItiS an object f this n n n to p ovide 3 products and i movi bed operations the' tprocess for the production of small, spheroidal alyst will be less susceptible to fracture and atp i l s or p ll ts of alumina catalyst. It is antrition than irregular or fragmentary shapes. th r object o this invention to Provide 8 P c- It is also desirable that the spheres be as small ess for-the production of alumina pellets having as practical operations will permit in order to a i r n ter than about one millimeter. obtain the benefit of large outside surface areas It s another e t of s invention to P d exposed to the reactants per unit volume of cata m d h r y Small, spheroidal particles or alyst. Further, in moving bed operations, such pellets of alumina ata yst ay be obtainedby as in fluid flow technique, small-pellets are essenthe process wherein alumina hydrosol is extruded tial in order to obtain proper movement of the into a Water-immiscible forming l y r r y n catalyst under the carrying effect of the gaseous an aqu ous s tt n lay r- It s ano j ct reactant stream, of this invention to prevent agglomeration of sol Spherical and spheroidal alumina particles or lobules at the interface between a water-impellets have been prepared by extruding a hymiscible fo n layer nd an aqu ous setting drosol of alumina through an orifice into a, body layer; other Objects f this v nti n will be of water-immiscible liquid, such as a mineral oil, apparent from the following d cription thereof. which overlies a body of aqueous solution con- In a da with t i e ti n, s a l'sphetainjng a material, such as ammonia, capable of roidal particles OI pellets Of alumina catalyst are setting or converting the alumina sol to a gel. Produced y forming mall globules of alumina Upon extrusion into the body of water-immiscible hydrosol i Water-immiscible ing ayer overliquid, the sol assumes a spherical form due to lying an aqueous s ttin layer and maintaining the surface tension between the sol and the in solution in said aqueous setting a r amat water-immiscible liquid. The sol spheres, being rial capable of reducing the differential in density more dense than the water-immiscible liquid, b tw en t e wo ay s andreducing the interdescend through the liquid, pass through the 40 facial tension between thetwo layers. interface, and then descend into the underlying. I have found that two factors are primarily 5 body of aqueous solution where they are set into responsible for causing agglomeration of small f gel spheres by the action of thevsetting or gelling globules of alumina sol at the interface between material. While this method of formingalumina a forming layer and a setting layer, namely, the

gel spheres is satisfactory for the formation of difference in density between the liquids eom- 3 prising the two layers and the tension of the interfacial boundary between the two layers.

As a result of my investigations, 1 have determined that the size of the globules formed in the forming layer is a function of the density of the alumina sol, the density of the forming layer, the size of the orifice through which the sol is extruded into the forming layer, and the pressure of the sol behind the oriflce. These conin density differential and lnterfacial tension, 11. more soluble alcohol, such as methanol, may be employed in admixture with the less soluble alcohol to achieve the desired result.

The amount of organic liquid to be dissolved in the aqueous setting layer will depend upon the extent to which the density differential and interfacial tension are to be reduced. This in turn will depend upon the size of alumina pellet desired, the

ditions once being fixed, the size of the globules 1 density of the sol, the density of the liquid emin the forming layer will also be fixed. I have also determined that the velocity at which the globules descend through the forming layer is a function of the density of the liquid comprising the forming layer and the density and size of the sol globules, as well as other physical factors including the viscosity of the liquid. Thus, these factors being fixed, the rate of descent of the globules through the forming layer will also be ployed for the forming layer, and the type and concentration of setting agent employed in the aqueous setting layer. Additionally, the various organic liquids diifer in their effect on the interfacial tension and, to a lesser extent, on the density differential. Accordingly, no general rule can be given which will indicate with exactitude the amount of organic liquid to be employed in every case. In each case, however, the amount fixed. However, when the globules reach the setto be employed can be a y determined y t ial.

ting layer, which of necessity has a greater density than the forming layer, their rate of descent will be lessened and the extent to which their velocity will be lessened will be a function of While the amount'of organic liquid to be employed in each case cannot be given with exactltude because of the multiplicity of factors involved, it has been found, however, that in most the difier c in density, or density merential, cases it is possible to obtain pellets having a diambetween the two layers. Thus, when small globules are formed in the forming layer as compared to relatively large globules, their rate of descent will be sufiiciently lessened upon reaching the eter of one millimeter or less by the process of the invention where the amount of organic liquid employed is sufficient to reduce the density differentiaal to a value which is less than about twice setting layer to permit a build-up or agglomera- 0 the Value given by the expression tion with the sol globules which follow in the less dense forming layer at a higher rate.

I have also determined, as a result of my investigations, that density differential is not the Ds-Dr=0.1400.0026

where Ds and Dr are the densities in grams per cubic centimeter of the setting and forming layonly factor rendering impossible the formation of ers respect v y. and 'Y is the a al tension -small s heroidal particlesof alum'ina gel by this method oTrmmtbr, as before mentioned, is the tension of the interfacial boundary between the two liquids. Thus, when small in dynes per centimeter after addition of the ---organic"liquid. Jfiner'e laF ger sized pellets are globules of sol reach the interfacial surface, their 40 pellets are desired, they may be obtained emrate of descent is lowered, or they are even halted, by the tension of the interfacial boundary thereby causing agglomeration or, at the least, distortion of the globules into non-spheroidal shapes. Materials satisfactory for reducing the density differential and interfacial tension are inert water soluble organic liquids. Included among the organic liquids are the low molecular weight aliphatic alcohols. Of these alcohols, I prefer to employ ethyl alcohol, normal propyl alcohol, or isopropyl alcohol. However, satisfactory results may be obtained with other low molecular weight alcohols such as methyl alcohol, normal butyl alcohol, secondary butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, para-isoamyl alcohol, etc. Other satisfactory inert water soluble organic liquids are the ketones such as acetone.

Ethyl alcohol, normal propyl alcohol, and isopropyl alcohol are economical and readily available, and also are quite soluble in water, permitting adjustment of density differential and interfacial tension over a wide range of values. Certain other alcohols, particularly normal butanol and secondary butanol, are not quite as soluble in water and therefore the extent to which they may be employed per se for adjusting density differential and interfacial tension is more limited. However, it is not necessary that the organic liquids be employed singly, but may be employed in admixture with each other. Accordingly, where normal butyl alcohol, secondary butyl alcohol, or other less soluble alcohol is employed, and sumcient amounts cannot be dissolved because of soiubilitylimitations toachieve a desired reduction ploying a larger amount of organic liquid.

Any suitable type of liquid or liquids may be employed as the forming layer. Satisfactory liquids are the mineral oils such as normal hexane, naphthas, kerosenes, or light lubricating oils. However, the size of the alumina globules is a function of the viscosity of the forming layer, large globules being formed in high viscosity liquids and smaller globules being formed in low viscosity liquids. Additionally, the size of the globules depends somewhat on the density of the alumina 501. Therefore, selection of a liquid for the forming layer with respect to its viscosity must be made taking into consideration the size of the pellets desired and the density of the sol employed. Generally, the lower viscosity liquids are more desirable.

The aqueous setting layer may contain any suitable type of setting agent. Suitable setting agents comprise basic materials such as ammonia or the various water soluble organic bases such as amines, for example, isoamylamine. Sufllclent basic material should be used in the aqueous setting layer to insure setting or gelation of the sol globules by the time they pass through the setting layer. When using ammonia, concentrations beween 1 and 5 per cent by weight have been found satisfactory, concentrations of ammonia higher than 5 per cent may also be used, as, for example, concentrations as gh as 15 or 20 per cent or even up to saturation, that is, about 28 per cent. However, it is generally desirable to avoid these higher concentrations for the reason that they tend to set liquid for reducing density differential and interfacial tension such that too high a concentration of ammonia will be present in the supernatant forming layer and under these conditions, the sol globules tend to set before they assume spheroidal shape.

Alumina hydrosol for use in the invention may be prepared by any of the methods known to the art. A satisfactory type of hydrosol may be prepared by p ptizing amalgamated aluminum metal in-an aqueous solution of a weak acid, such as one per cent by weight solution of acetic acid.

Amalgamation of the aluminum metal may be accomplishedby treating the metal with aqueous mercuric nitrate or other mercury salt, and after amalgamation, washing to remove the mercury salt. The density of the sol afiects the strength of the resulting alumina pellet and it is preferred to employ a sol having a density of at least one gram per cubic centimeter.

Following setting of the pellets in the setting layer, they may be removed and dried, as by suction filtration or by warming at temperatures up to about 100 0., or by both filtration and warming. Following drying, the pellets. are then activated by heating, as for example, by heating to about 450 C or 500 C. for a period of about four to eight hours. screened to uniform size, if desired.

After drying and heating, there will be a diminution in the size of the pellets ascompared with the size of the globules as originally formed ing upon the density offthe $01" for the most one day, and finally activated by heating at 500 The pellets then may be part. Thus, there may beya five fold difference 5 in the size..of the globula-formed in the farminglayer and the pellet obtained after heating and drying. Therefore, as is well understood in the art, to obtain desired pellet sizes this factor must be taken into consideration in selecting the size of the globules to be formed in the forming layer.

The following examples will be illustrative of the invention. In each example, an alumina hydrosol was prepared by peptizing amalgamated aluminum in a one per cent by weight solution of acetic acid in water. The sol was injected in lobules about three to four millimeters in diameter into a forming layer overlying an aqueous setting layer containing ammonia and various percentages of organic liquids reducing the density difierential and interfacial tension. The set pellets were removed from the setting layer,

filtered dry on a suction filter, dried at room temperature for two days and then at 100 0. for

C. for four hours. In each example, the activated alumina pellets as finally obtained had diameters of one millimeter or less. Table I gives the cone ditions for Examples 1 to 6.

Table 1 Setting Layer Example Forming Layer, Compo- Number nent weight Component Fsopropyl Alco- 21.

1 Normal Herane l3 Water 05.

Mineral on having 100 1 g v 2 viscosity of 24.6Oentk 5 smkes- Water 49.

Normal Propyl 67.

3.. Kerosene Almhol' 11 Water 31.

Normal Butyl 13.

Alcohol.

4 -.do MethylAlcohol. 4. Ammonia.'...... l2. i eiii s'm' I? ary u 6 ..do l' 12 Water 69.

Para-Isoamyl l0.

- Alcohol.

6 ..do Methyl Alcohol- 31. Ammonia 13.

Water 44.

Examples 7 to 12 are further illustrative ofthe invention. The procedures followed were the L fisdescribedabove in connection with Ex measured by determining the amount of force required to pull a platinum ring through the interface and substituting in the equation where w is the force in grams necessary to pull' Table II Formin La er Setting Layer 8 Y Inter. ear: m1

Component Density Component 2:2 Density Tensionthyl Alcohol 04. 2 7 Kerosene .810 Ammonia.-- .0 .860 4.28

Water 26.8 Ethyl Alcoho 87. 7 8 "do. .810 Ammonia.-. 4.3 .820 3.22-

Water 8, 0 Isopropyl Alcohol. 21. 9 9 Naphtha .765 Ammonia 13.1 .913 8.35

Water 65.0 Isopropyl Alcohol. 31.3 10 Kerosene .812 Ammonia l3. 5 .902 5.42

Water 55. 2 ficggdiiry Bgtyl Alcoh e y co 0 11 --do .814 Ammon m2 .926 5.46

Water 71.0 Amfnnn 34.0 12 .-do .810 Ammonia 13.4 .895 12.1 Water 52.6

Table II gives the conditions of Havin thus described my invention, it is to be understood that such description has been given by way of illustration and example only, and not by way of limitation, reference for the latter purpose being had to the appended claims.

I claim:

1.- The process of preparing spheroidal particles of alumina gel which comprises forming a hydrosol of alumina, maintaining a body of water-immiscible liquid above a body-of an aqueous solution of a base capable of converting said hydrosol to a gel, introducing said hydrosol to said body of water-immiscible liquid in a manner to produce sol globules whereby said globules assume spheroidal shape due to surface tension 5 and pass through the interface into said aqueous solution and are thereby caused to gel to form spheroidal particles of alumina hydrogel and maintaining in said aqueous liquid a substantial amount of an inert water soluble organic liquid capable of reducing the density difi'erential and the interfacial tension between the bodies of water-immiscible liquid and aqueous solution.

2. The process of claim 2 wherein the organic liquid is an aliphatic alcohol.

3. The process of claim 2 wherein the alcohol is ethyl alcohol.

4. The process of claim 2 wherein the alcohol is normal propyl alcohol.

5. The process of claim 2 wherein the alcohol 3 is isopropyl alcohol.

6. The process of preparing spheroidal particles of aluminamgeluhavingwaldhimi fir not greater than about one millimeter which comprises iorming a hydrosol of alumina, maintaining a body of water-immiscible liquid above a body of an aqueous solution of a base capable of converting said hydrosol to a gel, introducing said hydrosol to said body of water-immiscible liquid in a manner to produce sol globules or such 40 8 size that upon drying their diameter will be not greater than about one millimeter whereby said globules assume spheroidal shape due to surface tension and pass through the interface into 5 said aqueous solution and are thereby caused to gel to form spheroidal particles of alumina hydrogel and maintaining in said aqueous liquid an inert water soluble organic liquid capable oi reducing the density diflerential and the inter- 10 facial tension between the bodies or water-immiscible liquid and aqueous solution in amounts such that the difl'erence in densities of the two bodies is less than about twice the value given by the expression 0140-011026 where 'y is the interfacial tension.

7. The process of claim 8 wherein the organic liquid is an aliphatic alcohol.

8. The process of claim 7 wherein the alcohol 20 is ethyl alcohol.

9. The process of claim 7 wherein the alcohol is normal propyl alcohol.

10. The process oi. claim 7 wherein the alcohol is isopropyl alcohol.

JOSEPH U. MEBBENGR 0 file of this patent:

UNITED STATES PATENTS Number Name Date m.......a2,384,946 ,-Marisic Sept. 18, 1945 2,422,499 Pierce et a1." June 17, 1947 35 2,429,751 Gohr et al Oct. 28. 1947 OTHER REFERENCES Glasstone Text Book of. Phys. Chem., Van Nostrand, 1940, page 488. Copy in Scientific Library.

Certificate of Correction Patent No. 2,471,000.

May 24, 1949.

JOSEPH U. MESSENGER It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 29, for entiaal read ential; column 7, line 24, for the claim reference numeral 2" read 1;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 8th day of November, A. D. 1949.

THOMAS F. MURPHY,

Assistant flommissioner of Patents. 

